Substituted benzohydroxamates and their use as acaricides



United States Patent US. Cl. 424-230 8 Claims ABSTRACT OF THE DISCLOSURE A pesticidal composition comprising a pesticidally effective amount of a compound of the formula in which R is methyl or ethyl and R represents methyl, ethyl, propyl, allyl or cH --CI- CH.

This application is a divisional application of US. patent application Ser. No. 461,541, filed June 4, 1965, now US. Patent No. 3,352,899.

This invention relates to novel arylhydroxamates haviing high acaricidal activities, acaricidial compositions containing novel compounds, and further includes methods for combatting pests and especially for controlling mites with the said compositions, and provides as its primary object, in a manner as hereinafter set forth, novel acaricides having high acaricidal activities against adults and eggs of mites.

It is known that mites are one of the most harmful pests of various crops and orchard trees and resistance problems in mite control are now becoming serious for most of the commercial acaricides. With the increase of these resistant mites, it is desired to disclose and develop acaricidal compounds for mite control.

We have now found the novel compounds particularly valuable as acaricides and adapted to be used as active ingredients of acaricidal compositions for the control of mites including resistant species and populations.

The novel compounds which are provided by this invention are 3,6-dichloro-2-alkoxybenzohydroxamates of the formula C1 OR wherein R represents a lower alkyl radical and R represents a member selected from the group consisting of alkyl, and alkynyl radicals.

It is the advantages of the invention that the compounds of the invention have sufficient low phytotoxicity to use without any injury on living plants and extremely low mammalian toxicity.

The novel compounds 3,6-dichloro-2-alkoxybenzohydroxa-mates may be prepared by several methods. In a convenient method the compounds are prepared through the reaction of 3,6-dichloro-2-alkoxybensohydroxamic acid with reagents such as dialkyl sulfate, alkyl halides, alkenyl halides and alkynyl halides. This reaction is carried out in alcoholic aqueous solution in the presence of a dehydrochlorination agent such as alkali metal hy- 3,474,167 Patented Oct. 21, 1969 droxide and alkali metal carbonate. In an alternative method, the compounds may be obtained by reacting alkyl 3,6-dichloro-2-alkoxybenzoate with O-substituted hydroxylamines such as O-alkylhydroxylamines, O-alkenylhydroxylamines and O-alkynylhydroxylamines. This reaction is carried out in alcoholic solution in the presence of an equimolecular quantity of alkali metal alkoxide. In a further alternative method, the compounds may also be prepared by reacting 3,6-dichloro-Z-alkoxybenzoyl chloride with O-substituted hydroxylamines such as O-alkylhydroxylamines, O-alkenylhydroxylamines and O-alkynylhydroxylarnines. This reaction is carried out in an organic solvent in the presence of a dehydrochlorination agent such as tertiary amines and alkali metal carbonate.

The inventions illustrated by the following examples are not limitation thereof.

Example I A solution of 21.4 g. of 3,6-dichloro-Z-methoxybenzoyl chloride in 100 ml. of chloroform was added dropwise with vigorous stirring into a mixture consisting of 9.4 g. of O-methylhydroxylamine hydrochloride, 33.1 g. of potassium carbonate, 150 ml. of water and ml. of chloroform. The mixture was stirred at room temperature for further 5 hours, after which the layers were separated. The chloroform layer was washed with 50 ml. of diluted hydrochloric acid aqueous solution, and washed with 50 ml. of saturated aqueous solution of sodium bicarbonate after water washing, and then Washed with water. The washed chloroform solution was dried over magnesium sulfate, and then concentrated in vacuo. The residue gave 13.4 g. of the objective as white crystals, M.P. l17118 0., when recrystallized from benzene.

Example II (31 OCH About 40 ml. of an aqueous solution of 2.9 g. of potassium hydroxide and 0.5 g. of sodium carbonate was added to a cooled solution of 11.8 g. of 2,6-dichloro-2- methoxybenzohydroxamic acid and 7.8 g. of diethyl sulfate in ml. of methanol at a temperature of l5l7 C., with vigorous stirring, over a period of 5 minutes. The reaction mixture was stirred for additional 7 hours at a temperature of 20-30" C. The resulting mixture was concentrated in vacuo, and the residue was acidified with 1 ml. of conc-HCl and extracted with ml. of chloroform. The chloroform layer was Washed with 50 ml. of saturated aqueous solution of sodium bicarbonate, washed with water, and dried over magnesium sulfate. The dried chloroform solution was concentrated in vacuo. The residue gave 12 g. of the objective as white crystals, M.P. 1230-1245 C., after recrystallization from benzene.

Example III (|3-NH-OCH2CH-CH1 (1; O

To a cooled solution of 11.8 g. of 3,6-dichloro-2- methoxybenzohydroxamic acid and 6.7 g. of allyl bromide in 80 m1. of methanol was added 40 ml. of an aqueous solution containing 2.9 g. of potassium hydroxide and 0.5 g. of sodium carbonate at a temperature of 19-27 C., with vigorous stirring, over a period of 10 minutes. About 10.9 g. of the objective was obtained as white crystals with M.P. 93.594.5 C., in the manner described in Example II.

A part of compounds of the present invention is listed in table I, but the objectives of this invention are not limited only in these compounds.

This composition is diluted with water to give an aqueous dispersion suitable for use in accordance with the invention.

Example VI The following dust formulation can be prepared by blending of the active ingredients and inert diluent together and then grinding to be homogeneous powder.

IV -fiNHOCI-IzCH=CH ""410 93.5-94.5

Cl 0([JH3 V (|NIIOC1I:C-C1I do 117-118 VI (3NHOCIIzCH=CHg tlo 121-122 The compositions in the present invention include one or more of the aforesaid compounds and other pesticides, and are formulated in emulsifiable concentrates, dusts, wettable powders and aerosols.

Example IV The following composition is formulated as an emulsifiable concentrate by dissolving the active ingredient in a solvent together with a surface-active agent.

Parts Compound I 20 Alkylarylpolyoxyethylene 5 Xylene 75 A wettable powder having the following composition can be prepared by grinding together a mixture of the active ingredient, an inert diluent, a surface active agent and dispersing agent.

Parts Compound II 20 Higher alcohol sulfonate 5 Diatomaceous earth 75 Parts Compound III 2.5 1,l-bis(4-chlorophenyl)ethanol 2.5 Alkyl aryl polyoxyethylene 0.1 Talc 94.9

This composition is applied as a dust suitable for use in accordance with the invention.

Example VII Acaricidal activity, phytotoxicity and mammalian toxicity of the novel compounds of this invention are shown in Table II as following test results.

Activity to adults.Adult females of the citrus red mite (Panonychus citri) were reared on mandarin orange leaves put into petri dishes each other. Then, on the leaves the aqueous suspensions of wettable powders formulated in accordance with the Example V were sprayed respectively. Mortalities were counted after three days.

Activity to eggs-Mandarin orange leaves, on which eggs of citrus red mite (Panonychus citrz') were laid, were put into petri dishes. Then, the water suspensions were sprayed according to the above test method. Ovicidal activities were observed after eight days.

Table II Acan'cidal Acute Activity Phytooral Mortality, toxicity toxicity percent against for mice No.0i Dosage Kidney LDao Compound percent Adult Egg bean (mg/kg.)

0.025 100 100 non I 0.806 9% 3 non. 1,500 0. 25 10 1 non.-." H

0.806 10 non- 11600 0. 25 10 1 nonm 3 7 non 2,000 non"--. IV 32 gg 3% non..

non V 0.00s 96 82 non L500 Untreated 6 3 non What we claim is: 1. An acaricidal composition comprising an acaricidally effective amount of a compound of the formula in which R is methyl or ethyl and R is methyl, ethyl, propyl, allyl or CH2CECH, in combination with an inert carrier.

2. An acaricidal composition according to claim 1, in which R and R are each methyl.

3. An acaricidal composition according to claim 1, in which R is methyl and R is ethyl.

4. An acaricidal composition according to claim 1, in which R is methyl and R is n-propyl.

5. An acaricidal composition according to claim 1, in which R is methyl and R is allyl.

6. An acaricidal composition according to claim 1, in which R is methyl and R is CH2-CECH.

7. An acaricidal composition according to claim 1, in which the inert carrier is a finely divided solid.

8. An acaricidal composition according to claim 1, in which the inert carrier is an organic liquid.

References Cited UNITED STATES PATENTS 3,190,800 6/1965 Furst 260-453 XR 3,236,871 2/1966 Hinman et a1. 260453 ALBERT T. MEYERS, Primary Examiner V. D. TURNER, Assistant Examiner US. Cl. X.R. 424-298, 309 

